JPS61222116A - Forming method for deposit-film - Google Patents

Abstract

PURPOSE:To increase a film formation rate, to improve reproducibility and to equalize the quality of a film by introducing a compound containing carbon and halogen and an active species into a film forming space, operating heat energy to these substances, chemically reacting these substances and forming a deposit film on a base body. CONSTITUTION:Heat energy is worked to a compound containing carbon and halogen and an active species, which is shaped by a chemical substance for forming a film and activated by an activating space 123, under the coexistence of these substances in place of the generation of plasma in a film forming space 101 for shaping a deposit-film. Chemical interaction by these substances is generated, promoted or amplified, thus preventing an adverse effect by etching action, abnormal discharge action, etc. on the deposit-film being formed. Accordingly, the film can be formed at high speed, and reproducibility in film formation and the quality of the film are enhanced, thus equalizing the quality of the film while also enabling shaping the film on a base body 103 hardly having heat resistance.

Description

Detailed Description of the Invention [Field of Application of the Invention] The present invention relates to a carbon-containing deposited film, particularly a functional film, particularly a semiconductor device, a photosensitive device for electrophotography, a licenser for image input, an imaging device, an optical The present invention relates to a method suitable for forming an amorphous or crystalline deposited film used in an electromotive force element or the like.

[Prior art]

For example, attempts have been made to form an amorphous silicon film using vacuum evaporation, plasma CVD1, CVD method 1 reactive sputtering, ion blasting, photo-CVD, etc. In general, plasma CVD is widely used. It is used and corporatized.

Deposited films made of amorphous silicon have excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity including uniformity and reproducibility.
In terms of mass production, there is room to further improve the overall characteristics.

The reaction process in forming an amorphous silicon deposited film by the conventionally popular plasma CVD method is considerably more complicated than that of the conventional CVD method, and there are many aspects of the reaction mechanism that are unclear. In addition, there are many formation parameters for the deposited film (for example, substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure,
Due to the combination of these many parameters (reaction vessel structure, pumping speed, plasma generation method, etc.), the plasma sometimes becomes unstable, often having a significant adverse effect on the deposited film formed. Moreover, device-specific parameters must be selected for each device.
Therefore, the reality is that it is difficult to generalize the manufacturing conditions. On the other hand, in order to develop an amorphous silicon film that fully satisfies each of the electrical, optical, photoconductive, and mechanical properties, it is currently considered best to form it by plasma CVD. There is.

Depending on the application of the deposited film, it is necessary to fully satisfy the requirements of large area, uniform film thickness, and uniform film quality, and to achieve mass production with high reproducibility through high-speed film formation.
Forming an amorphous silicon deposited film using the plasma CVD method requires a large amount of equipment investment for mass production equipment, and the management items for mass production also become complex, the management tolerance narrows, and equipment adjustments are delicate. Since it is,
These have been pointed out as problems that should be improved in the future. On the other hand, with the conventional technology using the normal CVD method,
This method requires high temperatures, and a deposited film with practically usable properties has not been obtained.

As mentioned above, it is strongly desired to develop a method for forming an amorphous silicon film that can be mass-produced using low-cost equipment while maintaining its practically usable characteristics and uniformity. The same can be said of other functional films, such as silicon nitride films, silicon carbide films, and silicon oxide films.

The present invention eliminates the above-mentioned drawbacks of the plasma CVD method and provides a method for forming a deposited film in a prescribed manner without relying on conventional forming methods.

[Object of the invention and summary of disclosure]

The purpose of the present invention is to improve the characteristics, film formation speed, and reproducibility of the film to be formed, and to make the film uniform in quality. The object of the present invention is to provide a deposited film forming method that can be easily achieved.

The above purpose is to introduce a compound containing carbon and halogen into a film formation space for forming a deposited film on a substrate, and to chemically interact with the compound to activate the chemical substances generated from the film formation chemical. This is achieved by the deposited film forming method of the present invention, which is characterized in that a deposited film is formed on the substrate by introducing seeds and applying thermal energy to them to cause a chemical reaction.

[Embodiment]

In the method of the present invention, instead of generating plasma in a film forming space for forming a deposited film, in the coexistence of a compound containing carbon and halogen and active species generated from a chemical substance for film forming, By applying thermal energy to these.

causing or promoting chemical interactions,
Because of the amplification, the deposited film that is formed is not adversely affected by etching effects or other adverse effects such as abnormal discharge effects.

Further, according to the present invention, a more stable CVD method can be achieved by arbitrarily controlling the atmospheric temperature in the film forming space and the substrate temperature as desired.

In the present invention, the thermal energy used in the film forming space is applied to at least a portion of the film forming space near the substrate, or to the entire film forming space. There is no particular restriction on the heat source used, and conventionally known heating media such as heating by a heating element such as resistance heating, high frequency heating, etc. can be used. Alternatively, thermal energy converted from light energy can be used. Furthermore, if desired, light energy can be used in combination with thermal energy. Light energy can be applied to the entire substrate using an appropriate optical system, or can be selectively applied to only desired areas, so the formation position and thickness of the deposited film on the substrate can be controlled. This makes it easier to control the target.

One difference between the method of the present invention and the conventional CVD method is that it uses active species activated in advance in a space different from the film-forming space (hereinafter referred to as activation space). This makes it possible to dramatically increase the film formation rate compared to the conventional CVD method, and also to further reduce the substrate temperature during deposition film formation, making it possible to deposit films with stable film quality. Membranes can be provided industrially in large quantities at low cost.

In the present invention, the active species from the activation space introduced into the film forming space has a lifetime of 0.1 seconds or more, more preferably 1 second or more, and optimally from the viewpoint of productivity and ease of handling. 1
Those with a duration of 0 seconds or more are selected and used as desired, and the constituent elements of this active species constitute the components constituting the deposited film formed in the film forming space.

In the present invention, the compound containing carbon and halogen introduced into the film forming space is, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon are replaced with halogen atoms. , for example, CuY2u+2
(u is an integer of 1 or more, Y is at least one element selected from F, CI, Br, and I), CVY2V (V is an integer of 3 or more, Y
has the meaning given above. ) Cyclic halogenated carbon, CuHxYy (u and Y have the above meanings, x
+y=2u or 2u+2. ), and the like. Specifically, for example, CF
4, (CF2)5, (CF2)6, (CF2)4
．． C2FB, C3F8. CHF3°CH2F2. CCl
4. (CC12)s, CBr4. (CBr2)5,C
2C16, C2Br6. CHCl3. CHBr3. CH
Examples include those in a gaseous state or those that can be easily gasified, such as I3°C2Cl3F3.

Further, in the present invention, in addition to the above-mentioned compound containing carbon and halogen, a compound containing silicon and halogen can be used in combination. As the compound containing silicon and halogen, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used. Specifically, for example, 5iuZ2u+2 (U is one or more An integer, Z is at least one element selected from F, CI, Br, and I. Chain/chain halogenated silicon, 5iVZ2V (V is an integer of 3 or more, Z has the above meaning .) Cyclic/\ halogenated silicon, 5iuHxZy (u and Z have the meanings given above).

)c+y=2u or 2u+2. ), and the like.

Specifically, for example, 5fF4. (SiF2)5゜(SiF
2)6. (SiF2)4.5i2Fe.

Si3F8. SiHF3. SiH2F2゜5iC14,
(SiC1z)s, SiBr4゜(SiBr2)5,5
i2C1B, 5i2Br6, 5iHC13, 5iHBr
3.5iHI3, 5i2CI3F3 and the like which are in a gaseous state or can be easily gasified can be mentioned.

Furthermore, in addition to the above-mentioned compounds containing carbon and I\halogen (and compounds containing silicon and halogen), other silicon compounds such as simple silicon, hydrogen, halogen compounds (for example, F2 gas, O2 gas, Gasified Br2.I2, etc.) can be used in combination.

In the present invention, methods for generating active species in the activation space include microwave, R
Activation energy such as electrical energy such as F, low frequency, and DC, thermal energy such as heater heating, infrared heating, and light energy is used.

Activated species are generated by adding activation energy such as heat, light, electricity, etc. in an activation space to the above.

In the activation space used in the method of the present invention, the chemical substances for film formation that generate active species include hydrogen gas and/or halogen compounds (for example, F2 gas, C2 gas,
gases, gasified Br2, I2, etc.) are advantageously used. Furthermore, in addition to these chemical substances for film formation, an inert gas such as helium, argon, neon, etc. can also be used. When using multiple of these film-forming chemicals, they can be mixed in advance and introduced into the activation space in a gaseous state, or each of these film-forming chemicals can be supplied from an independent source. They can be supplied individually from each other and introduced into the activation space, or they can be introduced into independent activation spaces and activated individually.

In the present invention, the ratio of the amount of the active species to the compound containing carbon and halogen introduced into the film forming space depends on the film forming conditions,
Although it can be determined as desired depending on the type of active species, etc., it is preferably 10:1 to 1:10 (introduced amount ratio), and more preferably 8:2 to 4:6.

Further, the deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation. The impurity elements used include p-type impurities,
Elements of group m A of the periodic table, such as B, AI, Ga, In
, TI, etc. are mentioned as suitable ones, and as the n-type impurity, an element of Group V A of the periodic table, for example, P.

Preferred examples include As, Sb, Bi, etc.
In particular, B, Ga, P, Sb, etc. are optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical characteristics.

The substance containing such an impurity element as a component (substance for introducing impurities) is a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under deposited film forming conditions, and that can be easily vaporized with an appropriate vaporization device. Such compounds, which are preferably selected, include PH3, P2H4, PF3, PF5, PCl3
.

AsH3, AsF3. AsF5. AsCl3゜SbH3
, SbF5. SiH3, BF3. BCl3, BBr3
．． B2H6, B4H10, B5H9, B5H11, B6
Examples include H10, B6H12, Alct3, and the like. The compounds containing impurity elements may be used alone or in combination of two or more.

The impurity-introducing substance may be introduced into the film forming space directly in a gaseous state or mixed with the above-mentioned compound containing carbon and halogen, or it may be activated in the activation space and then introduced into the film forming space. It can also be introduced into In order to activate the impurity-introducing substance, the above-mentioned activation energy can be appropriately selected and employed. Active species (PN) generated by activating the impurity introducing substance are mixed with the active species in advance or are introduced independently into the film forming space.

Next, the present invention will be described with reference to typical examples of electrophotographic image forming members formed by the method of the present invention.

FIG. 1 is a schematic diagram for explaining an example of the structure of a photoconductive member as a typical electrophotographic image forming member obtained by the present invention.

The photoconductive member 1O shown in FIG. 1 can be applied as an electrophotographic image forming member, and includes an intermediate layer 1 provided as necessary on a support 11 for the photoconductive member.
2 and a photosensitive layer 13.

In manufacturing the photoconductive member 10, the intermediate layer 12 and/or the photosensitive layer 13 can be created by the method of the present invention. Furthermore, the photoconductive member 10 may include a protective layer provided to chemically and materially protect the surface of the photosensitive layer 13, or a lower barrier layer and/or an upper barrier layer provided for the purpose of improving electrical withstand pressure. If so, these can also be created by the method of the present invention.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, at, cr, and Mo.

Au, Ir, Nb, Ta, V, Ti, Pt.

Examples include metals such as P-d and alloys thereof.

Polyester is used as the electrically insulating support.

Films or sheets of synthetic resins such as polyethylene, polycarbonate, cellulose acetate, polypro, pyrene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Preferably, at least one surface of these electrically insulating supports is subjected to conductive treatment, and another layer is preferably provided on the conductive treated surface side.

For example, if it is glass, its surface is NfCr.

AI, Cr, Mo, Au, Ir, Nb, Ta.

V, Ti, I't, Pd, In2O3, 5n02゜IT
If it is conductive treated by providing a thin film such as O(In203+5n02) or a synthetic resin film such as polyester film, NiCr, AI, Ag
, Pb, Zn, Ni.

Au, Cr, Mo, Ir, Nb, Ta, V.

Vacuum evaporation, electron beam evaporation with metals such as Ti and Pt,
The surface is made conductive by sputtering or by laminating with the metal. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined depending on the need. For example, the photoconductive member 10 in FIG. If used as a member, in the case of continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape.

For example, a photosensitive layer 13 is applied to the intermediate layer 12 from the support 11 side.
This effectively prevents the inflow of carriers into the photosensitive layer 13 and causes the photocarriers generated in the photosensitive layer 13 by electromagnetic wave irradiation and moves toward the support 11 from the photosensitive layer 13 side to the support 11 side. It has the function of allowing easy passage.

This intermediate layer 12 is composed of amorphous carbon (hereinafter referred to as a-C(H,X)J) containing carbon atoms, hydrogen atoms (H), and/or halogen atoms (X) as constituent atoms. , as a substance that controls electrical conductivity,
For example, it contains a p-type impurity such as boron or an n-type impurity such as phosphorus (P). Furthermore, silicon atoms may be included for the purpose of improving film quality.

In the present invention, the content of substances controlling conductivity, such as B and P contained in the intermediate layer 12, is preferably o
', o o l~5X104atomic ppm
, more preferably 0.5 to IX11X104ato p
pm, preferably 1 to 5×103atOmiCppm.

The intermediate M12 has similar components to the photosensitive layer 13.

Alternatively, if they are the same, the formation of the photosensitive layer 13 can be performed continuously after the formation of the intermediate layer 12. In that case, the raw materials for forming the intermediate layer include a compound containing carbon and halogen, active species generated from film-forming chemicals introduced into the activation space, and optionally an inert gas and impurities. and active species generated from a gas of a compound containing the element as a component, respectively separately or mixed as appropriate, and introduced into the film forming space where the support 11 is installed,
By applying thermal energy, the support ll
The intermediate layer 12 may be formed thereon.

Yamari 111) M intuition 1 14 ↓ gshi l no I 4 0! ~1
0 IL, more preferably 40λ to 8 ends, optimally 50 to 5 IL.

The photosensitive layer 13 is made of an amorphous material (hereinafter referred to as rA-3i (H, It has both a charge generation function of generating photocarriers by irradiation with light and a charge transport function of transporting the charges.

The thickness of the photosensitive layer 13 is preferably as follows.

1 to 100, more preferably 1 to 80P, most preferably 2 to 80P
It is desirable that the thickness be 50μ.

The photosensitive layer 13 is a non-doped a-5i (H, It may contain a substance that
If the actual amount of the substance that governs the conductivity of the same polarity contained in the intermediate layer 12 is large, it may be contained in an amount much smaller than the actual amount.

In the case of forming the photosensitive layer 13, if it is formed by the method of the present invention, it is formed from a compound containing carbon and halogen in the film forming space and a chemical substance for film forming, as in the case of the intermediate layer 12. A support 11 is supplied with the active species to be treated, and if necessary, an inert gas, a gas of a compound containing an impurity element as a component, etc.
The intermediate layer 1 formed on the support 1 is introduced into the film forming space where the intermediate layer 1 is installed, and thermal energy is used.
What is necessary is to form a photosensitive layer 13 on 2.

FIG. 2 is a schematic diagram showing a typical example of a PIN type diode device using an A-3i deposited film doped with an impurity element, which is manufactured by carrying out the method of the present invention.

In the figure, 21 is a base, 22 and 27 are thin film electrodes, 23 is a semiconductor film, an n-type semiconductor layer 24, an i5 semiconductor layer 2
5. It is composed of a p-type semiconductor layer 26. The present invention can be applied to the production of any one of the semiconductor layers 24, 25 and 26, but the conversion efficiency can be particularly improved by producing the semiconductor layer 26 by the method of the present invention.
When forming the semiconductor layer 26 by the method of the present invention, the semiconductor layer 26 is made of an amorphous material (hereinafter rA-3ic (H,X)J). 28 is a conductive wire connected to an external electric circuit device.

The base 21 may be conductive, semiconductive, or electrically insulating. If the substrate 21 is conductive, the thin film electrode 22 may be omitted. Examples of semiconductive substrates include St 2 , Go 2 , GaAs, and ZnO.
, ZnS, and other semiconductors. Thin film electrode 22.27
For example, N iCr * A I + Cr
r M o *Au, Ir, Nb, Ta, V, Ti, P
t.

Pd, I n203.5n02, ITO (I n2
03 + S n 02 ) or the like on the substrate 21 by a process such as vacuum evaporation, electron beam evaporation, or sputtering. The thickness of the electrodes 22.27 is preferably 30 to 5×10 4 people, more preferably 100 to 5×10 3 people.

In order to make the film forming the semiconductor layer n-type or p-type as necessary, during layer formation, n-type impurity, p-type impurity, or both impurities are added to the layer to be formed. It is formed by doping while controlling the amount.

When forming n-type, i-type, and p-type semiconductor layers, any one layer or all of the layers can be formed by the method of the present invention. During film formation, a compound containing carbon and halogen and another compound containing silicon and halogen are introduced into the film formation space, and a chemical substance for film formation is introduced into the activation space as necessary. Accordingly, inert gases and compound gases containing impurity elements as components are excited and decomposed by activation energy to generate respective active species,
The layer thicknesses of the n-type and p-type semiconductor layers, which can be performed by introducing each separately or appropriately mixed and introducing them into the film-forming space where the support 11 is installed and applying thermal energy, are as follows: Preferably 100 to 104 people, more preferably 300 people
A range of ~2,000 people is desirable.

Further, the thickness of the i-type semiconductor layer is preferably 50
A range of 0 to 104 people, more preferably 1000 to 1000 people is desirable.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Fig. 3, 1 was carried out by the following operations.
Type, p-type, and n-type carbon-containing amorphous deposited films were formed.

In FIG. 3, 101 is a film forming chamber, and a desired substrate 103 is placed on a substrate support stand 102 inside.

104 is a heater for heating the substrate;
4 is used when heat-treating the base 104 before the film-forming process, or performing a 7-neal process to further improve the properties of the film formed after the film-forming process, and is supplied with power via the conductive wire 105. I get a fever.

The substrate temperature in carrying out the present invention is preferably 30 to 450°C, more preferably 50 to 350°C.

106 to 109 are gas supply sources, which include gases of chemical substances for film formation, and inert gases used as necessary;
It is provided depending on the type of compound gas containing an impurity element as a component. If these gases are liquid in their standard state, an appropriate vaporizer is provided.

In the figure, the gas supply systems 106 to 109 are marked with a for branch pipes, b for flowmeters, C for pressure gauges that measure the pressure on the high pressure side of each flowmeter, and d for gas supply systems 106 to 109. The ones marked with "e" are valves for adjusting the flow rate of each gas. 12
3 is an activation chamber for generating active species, and activation chamber 1
A microwave plasma generator 122 that generates activation energy for generating active species is provided around the plasma generator 23 . Raw material gas for active species generation supplied from the gas introduction pipe 11O is activated in the activation chamber 123, and the generated active species are transferred to the film forming chamber 10 through the introduction pipe 124.
1. 111 is a gas pressure gauge.

In the figure, 112 is a compound supply source containing carbon and halogen, and the ae attached to the symbol 112 are 106 to 109.
It shows something similar to the case of . A compound containing carbon and halogen is introduced into the film forming chamber 101 through the introduction pipe 113.

Reference numeral 117 denotes a thermal energy generating device, and for example, a normal electric furnace, a high frequency heating device, various heating elements, etc. are used.

The heat from the thermal energy generator 117 is.

It is added to the compound and active species containing carbon and /\rogen flowing in the direction of the arrow 119, and the added compound and active species chemically react with each other to form the substrate 10.
3 on a-C(H.

A deposited film of X) is formed. Further, in the figure, 120 is an exhaust valve, and 121 is an exhaust pipe.

First, a substrate 10 made of polyethylene terephthalate film
3 was placed on the support stand 102, and the inside of the film forming chamber 101 was evacuated using an exhaust device (not shown), and the pressure was reduced to approximately 1 (lfiTorr).
sccM was introduced into the activation chamber 123 via the gas introduction pipe 110. The H2 introduced into the activation chamber 123 was gasified into activated hydrogen and the like, and the activated hydrogen and the like were introduced into the film forming chamber 101 through the introduction pipe 124.

On the other hand, CF4 gas is introduced into the pipe 113 from the supply source 112.
After that, it was introduced into the film forming chamber 101.

While maintaining the internal pressure in the film forming chamber 101 at 0.4 Torr, the inside of the film forming chamber 101 was maintained at 205° C. using a thermal energy generator to form a carbon-containing namorphous film (thickness: 700 Torr). The film formation rate was 28λ/sec.

Next, the obtained carbon-containing amorphous film sample was placed in a vapor deposition tank, a comb-shaped AI gap electrode (gap length 250 l, width 5 mm) was formed at a vacuum degree of 10-5 Torr, and the dark current was measured at an applied voltage of 10 V. B: The film properties were evaluated by determining the dark conductivity σd. The results are shown in Table 1.

Embodiment 2 Instead of H2 gas from the gas supply cylinder 106 etc., H2/
F2 mixed gas (mixture ratio H2/F2=IC+) Moro:
1 1% J+ トIM Ij dy
4&m I L la ↓bud AN+ yu←
and carbon-containing amorphous a-C(H,X) according to the procedure
A film was formed. The dark conductivity of each sample was measured and the results are shown in Table 1.

Table 1 From Table 1, it was found that according to the present invention, a carbon-containing amorphous film having superior electrical properties, that is, a high σ value, could be obtained compared to the conventional method.

Example 3 Using the apparatus shown in Fig. 4, the first
A drum-shaped electrophotographic image forming member having a layer structure as shown in the figure was prepared.

In FIG. 4, 201 is a film forming chamber, 2o2 is a compound supply source containing carbon and halogen, 206 is an introduction pipe, 207 is a motor, 208 is a heating heater used in the same manner as 104 in FIG. Blowout pipe, 211 is A
The I cylinder-shaped body 212 represents an exhaust valve. Further, 213 to 216 are raw material gas supply cylinders similar to 106 to 109 in FIG. 3, and 217-1 is a gas introduction pipe.

An AI cylinder base 211 is suspended in the film forming chamber 201, a heater 208 is provided inside the base, and a motor 20 is installed.
7 so that it can be rotated. 218 is a thermal energy generating device, and for example, a normal electric furnace, a high frequency heating device, various heating elements, etc. are used.

Further, CFa gas was introduced from the supply source 202 into the film forming chamber 201 through the introduction pipe 206.

Further, SiF4 gas was introduced in the same manner from a supply source (not shown) having the same structure as the supply source 202.

On the other hand, H2 gas is introduced into the activation chamber 219 from the introduction pipe 217-1.
introduced within. In the activation chamber 219, the introduced H2 gas undergoes activation processing such as plasma generation by the microwave plasma generator 221, becomes activated hydrogen, and is introduced into the film forming chamber 201 through the introduction pipe 217-2. . At this time, impurity gases such as PH3 and B2H6 were also introduced into the activation chamber 219 for activation, if necessary. Film forming chamber 20
While maintaining the pressure inside film forming chamber 201 at 0.8 Torr, the inside of film forming chamber 201 is maintained at 205° C. by a thermal energy generator.

The A1 cylindrical substrate 211 was rotated and evacuated. In this way, the photosensitive layer 13 was formed.

Further, the intermediate layer 12 is
By introducing a mixed gas of H6 (0.2% B2H8 gas by volume), the film thickness was 2000! A film was formed.

Comparative Example 1 A film forming chamber having the same configuration as the film forming chamber 201 was prepared using CF4, S i F4, H2, and B2H6 gases.
An electrophotographic image forming member having the layer structure shown in FIG. 1 was formed by a general plasma CVD method equipped with a 3.56 MHz high frequency device.

Table 2 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 3 and Comparative Example 1.

Example 4 Using the apparatus shown in FIG. 3, the PI'N type diode shown in FIG. 2 was manufactured.

First, a polyethylene naphthalate film 21 on which 1000 ITO films 22 were deposited was placed on a support stand, and
After reducing the pressure to 8 Torr, CF4 and 5iFa were introduced into the film forming chamber 101 through the introduction pipe 113 in the same manner as in Example 3.

In addition, H2 gas and PH3 gas (100
0 ppm hydrogen gas dilution) were introduced into the activation chamber 123 and activated.

Next, this activated gas was introduced into the film forming chamber 101 via the introduction pipe 124.

The pressure inside the film forming chamber 101 is set to 0. ITorr, while keeping the deposition chamber temperature at 205°C, N-type a-3 doped with P
iC(H,X) film 24 (film thickness (Zr/lJ'V) II#
M 11A & li? 177% - 19 man knee 14/'/
Doped (1) a-5i C(H,X) film 25 (1114
5,000 people).

Next, along with H2 gas, B2H6 gas (1000pp
A p-type a-9iC (H, Furthermore, on this p-type film, an AI electrode 27 with a film thickness of 1000 layers is formed by vacuum evaporation, and the PI
An N-type diode was obtained.

I of the diode element thus obtained (area 1 cm2)
-V@ property was measured and rectification characteristics and photovoltaic effect were evaluated. The results are shown in Table 3.

In addition, regarding the light irradiation characteristics, light is introduced from the substrate side, and at the light irradiation intensity AMI (approximately 100 mW/cm2), the conversion efficiency is 8.5% or more, the open circuit voltage is 0.98 V, and the short circuit current is 10.4. mA/cm2 was obtained.

Example 5 IJIL+ using H2/F2 mixed gas (H2/F2=15) instead of H2 gas from the inlet pipe 110
*414A)-rFRmL: 1. -r-'El
Example A-P A PIN type diode similar to the one made by the inventor was fabricated.

This sample was evaluated for rectification characteristics and photovoltaic effect, and the results are shown in Table 3.

Table 3 Book 1 Forward current and reverse current at voltage 1V Kitamoto 2p
-n Junction (7) Current formula J=Js (exp (M)
From Table 3 of n value (Quality Factor) at -1, it was found that according to the present invention, an amorphous semiconductor PIN type diode having better optical and electrical characteristics than the conventional one can be obtained.

〔Effect of the invention〕

According to the deposited film forming method of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the formed film are improved, and high-speed film formation is possible. In addition, the reproducibility in film formation is improved, making it possible to improve film quality and make the film uniform. It is also advantageous for increasing the area of the film, improving film productivity and easily achieving mass production. be able to. Furthermore, since relatively low thermal energy is used as excitation energy, the film can be formed even on a substrate with poor heat resistance, and the process can be shortened by low-temperature treatment.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram for explaining an example of the structure of an electrophotographic image forming member manufactured using the method of the present invention. FIG. 2 is a schematic diagram for explaining an example of the configuration of a PIN diode manufactured using the method of the present invention. FIGS. 3 and 4 are configurations of an apparatus for carrying out the method of the present invention used in Examples, respectively. FIG. 2 is a schematic diagram for explaining. 10--An electrophotographic imaging member, 11--A substrate, 12--An intermediate layer, 13--M-Photosensitive layer. 21---One substrate, 22.27---Thin film electrode. 24---n type semiconductor, 25---i type semiconductor, 26---p type semiconductor, 101.201---1 film formation chamber, 123.219---1 activation chamber 106. 107,108,109,112゜202.2
13,214,215,216---Gas supply source, 103.211---A substrate, 117.218---A thermal energy generating device.

Claims (1)

[Claims] In a film forming space for forming a deposited film on a substrate, an active substance generated from a compound containing carbon and halogen and a film forming chemical that chemically interacts with the compound. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by introducing seeds and applying thermal energy to them to cause a chemical reaction.